Process of preparing cellulosic spinning solutions and soft-luster products thereof



Patented May 25 1937 UNITED STATES PATENT OFFICE PROCESS OF PREPARING CELLULOSIC SPIN- NING SOLUTIONS AND SOFT-LUSTER PRODUCTS THEREOF Rayon Corporation, New York, N. Y.,

ration of Delaware a corpo- No Drawing. Application August 13, 1934, Serial No. 739,636

14 Claims.

The present invention relates to a process of producing cellulosic spinning solutions and softluster products thereof of pleasing hand.

A short while after rayon yarns became durable and uniform enough to create a popular demand, it became evident that the high luster of fabrics woven from them, hitherto considered an advantage, was objectionable in many fabric constructions. The first delustered rayon to achieve any degree of commercial success was produced by causing the formation of small air bubbles inside the individual filament. Rayon delustered with oil, possessing more strength than the original air-delustered yarn became immediately popular. Subsequently other methods, for example the dispersing of pigments, such as titanium dioxide, etc., were introduced to modify the original luster of rayon products.

One object of our invention has to do with an emulsion of halogenated oils, fats, waxes and resins in cellulosic spinning solutions to form, after extrusion, filaments of subdued luster, said filaments retaining their tensile strength while having a pleasing hand.

Another object of our invention relates to the emulsification of chlorinated oils, fats, waxes and resins with cellulosic spinning solutions for the aforementioned purpose.

A third object of this invention relates to the incorporation of brominated oils, fats, waxes and resins into cellulosic spinning solutions, such as viscose and cuprammonium cellulose to form by extrusion dull-luster products.

A fourth object of our invention has to do with the dispersion of halogenated oils, fats, waxes and resins in combination with other lustermodifying agents, such as water-insoluble, inert solvents, pigments, etc., in cellulosic spinning solutions of the aforementioned type.

Other objects of our invention will become apparent to those skilled in the art after a study of the following specification.

We are well aware that it has, heretofore, been proposed to produce soft-luster, cellulosic products by incorporating therein fatty and mineral oils, paraffin, Montan wax, Halowax, chlorobenzene, etc., but we have unexpectedly found that the physical properties of such products can be increased by replacing the aforementioned substances with halogenated oils, fats, waxes, and resins. In addition, due to the fact that the halogenation of such substances results in denser compounds, it is possible to produce softluster products with relatively small amounts of delustering agents. In addition, the incorporation of our halogenated delustering agents not only improves the tensile strengths of softluster, cellulosic products in comparison to those heretofore attained, but it makes the production thereof more economical.

The halogenation of oils, fats, waxes and resins can be carried out with any of the well known methods,

The substances to be halogenated may, for example, be first dissolved in carbon tetrachloride and subsequently chlorine or bromine in gaseous form introduced therein until the heat of reaction abates. Halogenated compounds, containing about 25 to 40% of chlorine or bromine may be obtained in this manner. However, if the introduction of halogens is prolonged, solid and translucent bodies may be obtained containing up to about 75% of chlorine or bromine. It is to be noted in this connection that the fusing or boiling points of the raw materials are either lowered or raised by halogenation. When colophony, for example, is dissolved in carbon tetrachloride and chlorine introduced therein until the mixture has cooled down to room temperature, the final product contains about 20% of chlorine and it has a fusing point of about 94 C. If more chlorine is introduced at room temperature, reaction products containing about 60% of chlorine may be formed having a fusing point of about 115 C. Paraiiin, treated in this manner, results in products containing about 70% of chlorine, these products being able to resist attack by boiling nitric acid or strong caustic soda. Hydrochloric o-r hydrobromic acid, formed during the reaction, must be removed, preferably by neutralization. Catalysts, such as iron, etc., may be added to the mixture to accelerate halogenation. Halogenation will also proceed more rapidly by carrying out the reaction under exposure to ultra-violet rays.

The halogenation of oils, fats, waxes, and resins may also be performed in accordance with methods disclosed in U. S. Patents No. 989,225 to Blakeman of April 11, 1911; No. 1,191,916 to Brooks of July 18, 1916; No. 1,246,810 to Ellis of November 13, 1917; No. 1,432,761 to Koch of October 24, 1922; etc.

The halogenated substances may be emulsified in conventional viscose and cuprammonium cellulose solutions with or without the assistance of suitable emulsifying agents, such as soaps, ethylene, glycols, etc. They may also be dissolved in inert, volatile organic solvents and the resulting composition emulsified with the spinning solutions. Pigments, for example titanium dioxide, may be dispersed in dissolved or molten halogenated substances and these mixtures uniformly distributed in the viscose or cuprammonium cellulose solutions to modify'the luster of the finished products.

Example 1 About 1 to 10% of a halogenated oil, fat, wax or resin is emulsified in a conventional viscose solution, these percentages being based upon the cellulose content of the aforementioned solution. After extrusion into conventional spinning baths, more or less delustered filaments, ribbons, films, etc. of viscose may be obtained. If the halogenated substance selected is difficultly emulsifiable in the spinning solution, a proper distribution of its globules may be brought about with the assistance of suitable emulsifying agents, or it may first be dissolved in an inert, Water-insoluble hydrocarbon and the like to form a composition which subsequently is emulsified with the Viscose solution. A variation of this process consists in fusing a solid, halogenated substance, for example chlorinated paraffin, and distributing a finely ground pigment therein. The still liquid mixture is then emulsified with the spinning solution. Such highly chlorinated or brominated paraffins are especially suitable for diminishing the luster of viscose products. However, we wish to emphasize that our invention is not limited to' the use of chlorinated or brominated paraflin. The following table depicts a number of substances which, after halogenation, become improved delustering agents for rayon:

Oils.O1ive oil, cottonseed oil, Chinese-wood oil, linseed oil, castor oil, hemp oil, poppy oil, soya bean oil, pumpkin oil, bone oil, paraflin oil, mineral oils, asphalt oils, machine oil, turpentine, pine oil, etc.

Fats-Lard, lanoline, beef tallow, suet, etc.

Waxes.-Carnauba Wax, candelilla wax, beeswax, insect wax, cetaceum, ozocerite, solid paraffin, neftigil, ceresin, Vaseline, Montan wax, etc.

Resins.Rosin, condensation resins, etc.

From the above it will be seen that we can use vegetable, animal and mineral oils, vegetable and animal fats, vegetable, animal and mineral waxes, and natural and synthetic resins, which produce, after halo'genation, improved agents for delustering cellulosic products.

Example 2 Instead of incorporating the aforementioned, halogenated substances into viscose spinning solutions, they are emulsified with cuprammonium cellulose solutions. The percentages and compounds enumerated in Example 1 may be used in connection with cuprammonium cellulose to form soft-luster products therefrom.

We wish to point out that the above examples are merely illustrative, and we do not wish to be limited to the exact proportions, set forth above, which are typical combinations, as certain of these compounds may be omitted or replaced by others of similar nature, and the proportions within wide limits may be varied. In other words, while we have found that the halogenated compounds above mentioned give the desired results, we do not wish to be limited to the use of all of these compounds, to these compounds and no others, nor to the exact proportions and concentrations, set forth above, as a considerable variation of proportions will not adversely affect the final products, although it may vary somewhat the relative characteristics of such products, resulting from such variations. Modifications will manifest themselves to those skilled in the art without departing from the spirit and scope of our invention, as defined by the appended claims.

We wish to emphasize, however, that only such halogenated compounds are contemplated which are stable in alkaline and acid solutions while being substantially insoluble therein, that the term cellulosic solutions is limited to viscose and cuprammonium cellulose solutions, that the term halogenated substances embraces only chlorinated and brominated compounds and not iodinated and fluorinated ones, that the term waxes does not include aromatic compounds, such as halogenated naphthalenes, etc., sold under the trade-name Halowax, and that the appended claims should be read with these limitations.

We claim:

1. A spinning solution for the manufacture of soft-luster products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose a sufficient amount of a chlorinated parafiin to diminish the luster of the products spun from said solution.

2. A spinning solution for the manufacture of soft-luster products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose a suflicient amount of a brominated parafiin to diminish the luster of the products spun from said solution.

3. A spinning solution for the manufacture of soft-luster cellulosic products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose and about 1 to 10 per cent of a chlorinated paraffin, said percentages being based upon the cellulose content of said solution.

4. A spinning solution for the manufacture of soft-luster cellulosic products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose and about 1 to 10 per cent of a brominated paraflin, said percentages being based upon the cellulose content of said solution.

5. A soft-luster cellulosic product selected from the group consisting of viscose and cuprammonium cellulose containing a substance selected from the group consisting of chlorinated and brominated paraffins in sufficient amount to diminish the luster thereof.

6. A spinning solution for the manufacture of soft-luster products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose together with a suflicient amount of wax selected from the group consisting of chlorinated vegetable waxes, brominated vegetable waxes, chlorinated animal waxes, brominated animal waxes, chlorinated paraflins and brominated paraifins to diminish the luster of the products spun from said solution.

7. A spinning solution for the manufacture of soft-luster products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose together with a sufiicient amount of a chlorinated animal wax to diminish the luster of the products spun from said solution.

8. A spinning solution for the manufacture of soft-luster products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose together with a sumcient amount of a chlorinated animal wax.

9. A spinning solution for the manufacture of soft-luster products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose together with about 1 to 10% of a wax selected from the group consisting of chlorinated vegetable waxes, brominated vegetable waxes, chlorinated animal waxes, brominated animal waxes, chlorinated paraifins and brominated paraflins, said percentages being based upon the cellulose content of said solution.

10. A spinning solution for the manufacture of soft-luster products comprising a cellulosic solu-- tion selected from the group consisting of viscose and cuprammonium cellulose together with about 1 to 10% of a chlorinated vegetable wax, said percentages being based upon the cellulose con-= tent of said solution.

11. A spinning solution for the manufacture of soft-luster products comprising a cellulosic solution selected from the group consisting of viscose and cuprammonium cellulose together with about 1 to 10% of a chlorinated animal wax, said percentages being based upon the cellulose content of said solution.

12. A soft-luster, cellulosic product selected from the group consisting of viscose and cuprammonium cellulose containing a finely dispersed wax selected from the group consisting of chlorinated vegetable Waxes, brominated vegetable waxes, chlorinated animal waxes, brominated animal waxes, chlorinated paraffins and brominated paraifins said wax being present in sufiicient amount to diminish the luster.

13. A soft-luster, cellulosic product selected from the group consisting of viscose and cuprammonium cellulose containing a finely dispersed chlorinated vegetable wax in sufficient amounts to diminish the luster.

14. A soft-luster, cellulosic product selected from the group consisting of viscose and cuprammonium cellulose containing a finely dispersed chlorinated animal wax in sumcient amounts to diminish the luster.

THOMAS H. BYRON. RUDOLPH S. BLEY. 

